Inclusion of an anion guest within a molecular host formed by (4,6-dimethyl-1,3-phenylene)bis( N , N-dibenzylmethane) and [CuCl 4]2-/[TeCl6]2- through second-sphere coordination

Article abstract of DOI:10.1080/00958972.2011.592941

In this work, we have utilized the second-sphere coordination approach toward the construction of supramolecular inclusion solids Cl 2H₂O [H₂L₁]_0.5 [CuCl₄]_0.5 (Crystal 1) and Cl [H₂

Full text of DOI:10.1080/00958972.2011.592941

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Inclusion of an anion guest within
a molecular host formed by (4,6-
dimethyl-1,3-phenylene)bis( N , N
-dibenzylmethane) and [CuCl4]2-/
[TeCl6]2- through second-sphere
coordination
Fang Guo a , Shuang Zhang a , Hong-Yu Guan a , Na Lu a & Wen-
Sheng Guo a
a College of Chemistry, Liaoning University, Shenyang 110036, P.R.
China
Version of record first published: 07 Jul 2011.
To cite this article: Fang Guo , Shuang Zhang , Hong-Yu Guan , Na Lu & Wen-Sheng Guo (2011):
Inclusion of an anion guest within a molecular host formed by (4,6-dimethyl-1,3-phenylene)bis(
N , N -dibenzylmethane) and [CuCl4]2-/[TeCl6]2- through second-sphere coordination, Journal of
Coordination Chemistry, 64:13, 2223-2233
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Journal of Coordination Chemistry
Vol. 64, No. 13, 10 July 2011, 2223–2233
Inclusion of an anion guest within a molecular host formed by
(4,6-dimethyl-1,3-phenylene)bis(N,N-dibenzylmethane) and
[CuCl4]2Z/[TeCl6]2Z through second-sphere coordination
FANG GUO*, SHUANG ZHANG, HONG-YU GUAN,
NA LU and WEN-SHENG GUO
College of Chemistry, Liaoning University, Shenyang 110036, P.R. China
(Received 11 February 2011; in final form 4 May 2011)
In this work, we have utilized the second-sphere coordination approach toward the
construction of supramolecular inclusion solids Cl ꢀ 2H2O ꢁ [H2L1]0.5 ꢀ [CuCl4]0.5 (Crystal 1)
and Cl ꢁ [H2L1] ꢀ [TeCl6]0.5 (Crystal 2). The chloride anions can be encapsulated inside the host
assemblies formed by the diamine molecule (4,6-dimethyl-1,3-phenylene)bis(N,N-dibenzyl-
methane) (L1) and the metal complexes ([CuCl4]2ꢂ and [TeCl6]2ꢂ
) via second-sphere
coordination. The complexes have been structurally characterized by X-ray crystallography,
indicating that weak C–H ꢀ ꢀ ꢀ Cl hydrogen-bonding synthons play a significant role in the
construction of second-sphere coordination complexes. 2-D networks are formed in both
complexes by the interconnection of 1-D networks through multiple C–H ꢀ ꢀ ꢀ Cl hydrogen-
bonding interactions with [CuCl4]2ꢂ and [TeCl6]2ꢂ. The guest chlorides are encapsulated inside
the host cages through N–H ꢀ ꢀ ꢀ Cl hydrogen bonds.
Keywords: Anion recognition; Second-sphere coordination; Supramolecular chemistry; X-ray
crystallography; [CuCl4]2ꢂ/[TeCl6]2ꢂ
1. Introduction
Molecular recognition directed by anion receptors has emerged as a major area in
supramolecular chemistry [1–3], partly because anions play many essential roles in the
environment, industrial, and health-related perspectives [4]. The synthesis of supramo-
lecular solid-state structures with various hosts including anion guest species in the
crystalline phase is a subject of intense investigation [5–8]. The binding of anionic
species to a host molecule may occur by one of the three effects or act in combination:
electrostatic attraction by cationic centers, formation of polar bonds with Lewis-acid
centers, and formation of hydrogen bonds.
Recently, the second-sphere coordination approach [9, 10] toward the construction
of supramolecular coordination polymers has attracted much attention as they offer
*Corresponding author. Email: fguo@lnu.edu.cn
Journal of Coordination Chemistry
ISSN 0095-8972 print/ISSN 1029-0389 online ß 2011 Taylor & Francis
DOI: 10.1080/00958972.2011.592941

2224
F. Guo et al.
H2
C
H2
C
H2
C
H2
C
N
N
H2C
CH3
H2C
H3C
Scheme 1. Scheme of L1.
intriguing possibilities for the inclusion and aggregation of guest molecules [11–15],
and as well exhibit intriguing architectures and topologies [16–18].
Second-sphere coordination refers to any intermolecular interactions with the primary
coordination sphere of a metal ion [10], in which choice of metal with specific
coordination geometries and the suitable design of ligands are key steps in the
production of second-sphere coordination complexes. Based on the second-sphere
coordination approach, some remarkable supramolecular inclusion complexes with
different guest encapsulations have been reported; however, the inclusion of more
sophisticated guest molecules or anionic species by exploiting specific host frameworks
has thus far been relatively rarely reported [19].
To achieve such inclusion systems, we have recently focused on the design of diamine
ligands with metal chloride salts MCl2 to obtain second-sphere coordination complexes
so as to encapsulate varieties of aromatic guest molecules [20]. In this work, we report
successful employment of second-sphere coordination approach into the construction
of host frameworks to trap the anionic guest. (4,6-Dimethyl-1,3-phenylene)bis(N,N-
dibenzylmethane) (L1, scheme 1) has been synthesized with the following structural
features: (1) the two NH functional groups are easily protonated, (2) the NH functional
groups are wrapped by five benzyl rings and two acidic N–H protons can be oriented in
a centripetal fashion, and (3) the two substituent benzylamine rings are spaced by the
˚
core 2,4-dimethylbenzene, with N ꢀ ꢀ ꢀ N distance around 5.5 A. The doubly protonated
ligand L1 serves as a building block because they can offer two positive charges
allowing strong electrostatic charge–charge interactions with anions; moreover, the
acidic protons are divergently oriented and are capable of forming a hydrogen-bond
chelate.
The tetrahedral [CuCl4]2ꢂ or octahedral [TeCl6]2ꢂ are selected as the primary
coordination sphere for two reasons: (1) they serve as hydrogen-bonding acceptors
to react with L1 through second-sphere coordination and (2) they can provide a
precise positioning within molecular assemblies by locating the special position of
crystallography. Thus the bulky benzyl rings in L1 can construct layers or channels,
generating a suitable size of cavity or void space accessible to anion guest
molecules.
Following the above design, supramolecular inclusion solids were constructed by a
second-sphere coordination approach. Chloride guest can be included, leading to the
formation of Cl ꢀ 2H2O ꢁ [H2L1]0.5 ꢀ [CuCl4]0.5 (Crystal 1) and Cl ꢁ [H2L1] ꢀ [TeCl6]0.5
(Crystal 2).

Supramolecular inclusion solids
2225
2. Experimental
2.1. Materials and measurements
All chemicals were analytical reagents and commercially purchased. IR spectra were
1
obtained with a Perkin Elmer 100 FT-IR spectrometer using KBr pellets. H NMR
spectra were recorded on a Mercury-Plus 300 spectrometer (VARIAN, 300 MHz) at
25ꢃC with TMS as the internal reference. Elemental analysis was obtained with a
Thermo Electron SPA, Flash EA 1112.
2.2. Preparation of L1
2.2.1. Synthesis of 1,5-bis(chloromethyl)-m-xylene. 10 g anhydrous ZnCl2, 200 g form-
aldehyde, 106 g m-xylene, and 300 mL concentrated hydrochloric acid were mixed and
refluxed at 90ꢃC for 12 h. After cooling overnight, the white precipitate was isolated by
filtration. The product is 121 g, yield 60%. Recrystallization from ethanol gave white
needle crystals, m.p. 94–98ꢃC [21, m.p. 96–98ꢃC]. IR (KBr, cmꢂ1): 2973 (s), 2924 (m),
1
1618 (m), 1506 (s), 1451 (s), 1375 (m), 902 (s), 801 (s), 656 (vs); H NMR (CDCl3,
300 MHz), ꢀ: 2.385 (s, 6 H, CH3), 4.571 (s, 4 H, CH2), 7.046 (s, 1 H, ArH), 7.251 (s, 1 H,
ArH). Elemental analysis (%): C, 59.14; H, 5.96 calculated from C10H12Cl2, observed:
C, 59.01; H, 5.97.
2.2.2. Synthesis of (4,6-dimethyl-1,3-phenylene)bis(N,N-dibenzylmethane) (L1). About
3.5 g NaHCO3, 4 mL H2O and 11.5 mL dibenzylamine were mixed and heated to 45ꢃC.
1,5-Bis(chloromethyl)-m-xylene (6 g) was then added and the solution was refluxed at
95ꢃC for 4 h. The reaction was cooled to room temperature and a white precipitate was
formed, 12 g, yield 65.4%, m.p. 100–104ꢃC. IR(cmꢂ1)ꢁmax(KBr): 3062.22, 3027.44,
1602.15, 1494.07, 1451.99; 908.87 (s, Ar–CH), 2925, 2880, 1470 (s, CH2),
1366.37 ꢄ 1246.35 (Ar–NH); 2918.83, 2794.02 (CH3); no absorption at 3500–3300,
1
suggesting the existence of tertiary amine. H NMR (CDCl3, 300 MHz), ꢀ: 6.846 (1 H,
ArH), 7.625 (1 H, ArH), 7.201–7.334 (20 H, ArH), 3.486 (12 H, CH2), 2.176 (6 H, CH3).
.
.
2.3. Preparation of Cl 2H2O ꢀ [H2L1]0.5 [CuCl4]0.5 (Crystal 1)
About 0.131 g L1 and 20 mL ethanol were placed in a 50 mL Erlenmeyer flask and
shaken until the contents dissolved; then 5 mL distilled water, 1 mL concentrated
hydrochloric acid, and 4 mL solution of Na2[CuCl4] were added and the flask was
allowed to stand for 2 days at room temperature. After the crystals were separated by
filtration, recrystallization from ethanol gave yellow, transparent block crystals, yield
75%, m.p. 170ꢃC–174ꢃC. IR(cmꢂ1)ꢁmax(KBr): 3060.43, 3032.96, 3005.49 (s, ArC–H),
1
2957.30, 2712.56 (s, CH2), 2592.87 (s, NHþ), 1640.93, 1499.13 (s, ArC–C); H NMR
(CDCl3, 300 MHz); ꢀ: 1.809 (6 H, CH3), 2.635–4.553 (12 H, CH2), 6.990–8.762 (22 H,
ArH), 10.782 (2 H, s, NHþ).

2226
F. Guo et al.
.
2.4. Preparation of Cl ꢀ [H2L1] [TeCl6]0.5 (Crystal 2)
The same experimental procedure as for Section 2.3 was carried out, with 0.4 mL
solution of Na2[TeCl6] added and the flask was allowed to stand for 3 days at room
temperature. After the crystals were separated by filtration, recrystallization from
ethanol gave yellow-green, transparent crystals, yield 70%, m.p. 238–241ꢃC.
IR(cmꢂ1)ꢁmax(KBr): 3062.77, 3035.03 (s, ArC–H), 2930.23 (s, CH2), 1622.70, 1499.47,
1456.00 (s, ArC–C); 1H NMR (D3CSOCD3, 300 MHz); ꢀ: 2.113(6 H, CH3),
4.202 ꢄ 4.382(12 H, d, CH2), 7.055 ꢄ 8.036 (22 H, m, ArH), 10.788 (2 H, s, NHþ).
2.5. X-ray crystallography
Single-crystal X-ray diffraction measurements of complexes were carried out on a
Bruker Smart CCD diffractometer equipped with a graphite-monochromator at 294 K.
The determination of unit cell parameters and data collection were performed with
˚
Mo-Kꢂ radiation (ꢃ ¼ 0.71073 A). The unit cell parameters were obtained with least-
squares refinements and the structures were determined using direct methods and
refined (based on F2 using all independent data) by full-matrix least-squares methods
(SHELXTL 97) [22]. Data were reduced by using the Bruker SAINT software. All non-
hydrogen atoms were refined with anisotropic displacement. Crystal data, refinement
details, and data collection parameters are given in table 1.
Table 1. Crystal data and refinement summary for 1 and 2.
1
2
Formula
C38H46Cl3N2O2Cu0.5
700.89
294(2)
Monoclinic
C2/c
C38H42N2Cl4Te0.5
732.34
293(2)
Formula weight
Temperature (K)
Crystal system
Space group
Triclinic
ꢀ
P1
ꢃ
˚
Unit cell dimensions (A,
)
a
b
c
ꢂ
ꢄ
ꢅ
22.391(5)
13.636(4)
26.077(6)
90
95.039(4)
90
7931(3), 4
1.174
0.866
11.066(3)
12.2176(13)
14.084(3)
98.715(14)
95.58(2)
101.334(18)
1829.5(7), 2
1.503
3
˚
Volume (A ), Z
Calculated density Dx (g cmꢂ3
)
Absorption coefficient, ꢆ (mmꢂ1
F(000)
)
1.141
840
3636
0.28 ꢅ 0.24 ꢅ 0.20
Crystal size (mm3)
Rint
0.37 ꢅ 0.35 ꢅ 0.23
0.0341
7004
0.0267
4781
No. of collected data (unique)
No. of data with I 4 2ꢇ(I)
No. of refined parameters
Rf/wRf
All data Rf/wRf
Goodness-of-fit
CCDC reference numbers
4492
413
0.0487/0.1360
0.0772/0.1474
1.054
3995
409
0.0460/0.1180
0.0587/0.1289
1.056
752171
752172

Supramolecular inclusion solids
2227
3. Results and discussion
3.1. Structure description of 1
The crystal 1 forms in the C2/c space group of monoclinic crystal system. The Cu is
located at crystallographic inversion centers and L1 are in a general position. One
asymmetric unit of 1 consists of one [L1]2Hþ, one Clꢂ, half of [CuCl4]2ꢂ, and two water
molecules (figure 1a). Through symmetry operations of the inversion center, Cu(II) is
˚
tetrahedrally coordinated by four chlorides with bond lengths of Cu1–Cl1 ¼ 2.253(1) A
ꢃ
ꢃ
˚
and Cu1–Cl2 ¼ 2.224(1) A. The Cl–Cu–Cl bond angles are 95.63(4) and 140.42(4) .
(a)
(b)
Figure 1. (a) Crystal structure of 1; (b) encapsulation assembly formed by neighboring ligand; (c) the
formation of 1-D molecular layer along the ab plane; and (d) crystal packing of 1 along the b-axis. For the
sake of clarity only hydrogens involved in H-bonding are represented.

2228
F. Guo et al.
(c)
(d)
Figure 1. Continued.
The crystallographically unique chloride is held in place between two protonated
nitrogens of the same ligand. The localization of two acidic protons on L1 and the
˚
N ꢀ ꢀ ꢀ N distance of 5.58(1) A between two nitrogens ensures recognition between
chloride and the protonated ligand through dihapto N–H ꢀ ꢀ ꢀ Cl interactions [N–H ꢀ ꢀ ꢀ Cl
ꢃ
˚
˚
hydrogen bonds (N1–H1 ꢀ ꢀ ꢀ Cl3: 3.285(1) A, 169.15 ; N2–H2 ꢀ ꢀ ꢀ Cl3: 3.275(1) A,
170.50ꢃ)]. Two neighboring L1 molecules construct anꢃencapsulation assembly by van
˚
der Waals force (C36–H36 ꢀ ꢀ ꢀ C4: 3.769(1) A, 132.2(1) , figure 1b). In addition to the
encapsulation of two Clꢂ’s, the two disordered water molecules encapsulate inside the
˚
assembly by self-association through O–H ꢀ ꢀ ꢀ O interactions (O1 ꢀ ꢀ ꢀ O2 ¼ 2.796(1) A,
˚
O1 ꢀ ꢀ ꢀ O1 ¼ 2.749(1) A). The approximate region for the inclusion of guest molecules is
˚
˚
6.9 A (defined by H23 and H2A) ꢅ 4.0 A (defined by H13 and H14).
The interconnection between the encapsulation assemblies through weak C–H ꢀ ꢀ ꢀ ꢈ
interactions [C24–H24B ꢀ ꢀ ꢀ C17: 3.573 A, 130.4ꢃ, H24 ꢀ ꢀ ꢀ C17 ¼ 2.867 A; C24–
˚
˚
ꢃ
˚
˚
H24B ꢀ ꢀ ꢀ C19: 3.741 A, 147.5 , H24B ꢀ ꢀ ꢀ C19 ¼ 2.887 A] leads to an infinite 1-D
molecular layer along the ab plane (figure 1c). These 1-D networks are further connected
into a 2-D network (figure 1d) through multiple C–H ꢀ ꢀ ꢀ Cl hydrogen-bonding

Supramolecular inclusion solids
2229
ꢃ
˚
Table 2. Selected weak C–H ꢀ ꢀ ꢀ Cl hydrogen bonding lengths (A) and angles ( ) for 1 and 2.
D
A
d(D–H)
d(H ꢀ ꢀ ꢀ A)
d(D–A)
ffDHA
1
C1
Cl1 (x, y, z)
Cl1 (x, y, z)
Cl2 (1 ꢂ x, 1 ꢂ y, 1 ꢂ z)
Cl2 (1 ꢂ x, 1 ꢂ y, 1 ꢂ z)
Cl1 (1 ꢂ x, 1 ꢂ y, 1 ꢂ z)
Cl1 (1 ꢂ x, 1 ꢂ y, 1 ꢂ z)
0.970
0.971
0.970
0.969
0.970
0.929
2.804
2.872
2.897
2.754
2.868
2.860
3.685
3.748
3.801
3.683
3.797
3.680
151.5
150.6
155.5
160.8
160.7
147.8
C15
C24
C25
C32
C34
2
C3
C8
C22
C38
Cl3 ( ꢂ x, ꢂ y, 1 ꢂ z)
0.93
2.836
2.770
2.892
2.874
3.670
3.713
3.785
3.738
149.8
163.9
155.1
154.9
Cl2 ( ꢂ x, ꢂy, 1 ꢂ z)
0.971
0.960
0.930
Cl2 (ꢂ1 þ x, ꢂ1 þ y, z)
Cl3 (ꢂ1 ꢂ x, ꢂ1 ꢂ y, 1 ꢂ z)
D, donor; A, acceptor.
interactions with [CuCl4]2ꢂ. The chloride of the long Cu1–Cl1 bond is a hydrogen-bond
acceptor, participating in four C–H ꢀ ꢀ ꢀ Cl interactions, two of which with two methylene
groups attach to the same NH in one molecule of ligand at (x, y, z) [C1–H1B ꢀ ꢀ ꢀ Cl1:
ꢃ
ꢃ
˚
˚
˚
3.687 A, 151.4 , H1B ꢀ ꢀ ꢀ Cl1 ¼ 2.805 A; C15–H15B ꢀ ꢀ ꢀ Cl1: 3.747 A, 150.6 , H15B ꢀ ꢀ ꢀ
˚
Cl1 ¼ 2.871 A] and the other two with one methylene and CH in one phenyl ring of the
ꢃ
˚
ligand at (1 ꢂ x, 1 ꢂ y, 1 ꢂ z) [C32–H32B ꢀ ꢀ ꢀ Cl1: 3.799 A, 160.8 , H32B ꢀ ꢀ ꢀ Cl1 ¼
ꢃ
˚
˚
˚
2.869 A; C34–H34 ꢀ ꢀ ꢀ Cl1: 3.679 A, 147.7 , H34 ꢀ ꢀ ꢀ Cl1 ¼ 2.858 A]. The other chloride
(short Cu1–Cl2 bond) is a hydrogen-bond acceptor involving two C–H ꢀ ꢀ ꢀ Cl interac-
tions with the methylene attached to the same NH of ligand at (1 ꢂ x, 1 ꢂ y, 1 ꢂ z) [C25–
ꢃ
˚
˚
˚
H25A ꢀ ꢀ ꢀ Cl2: 3.683 A, 160.8 , H25A ꢀ ꢀ ꢀ Cl2 ¼ 2.752 A; C24–H24A ꢀ ꢀ ꢀ Cl2: 3.800 A,
ꢃ
˚
155.5 , H24A ꢀ ꢀ ꢀ Cl2 ¼ 2.895 A]. As a result of crystal symmetry, the overall hydrogen-
bonding number around the metal complex is 12 (table 2).
3.2. Structure description of 2
ꢀ
Complex 2 was crystallized in a triclinic crystal system P1. One asymmetric unit of 2
contains one complete ligand, half of [TeCl6]2ꢂ, and one Clꢂ (figure 2a). Te lies on a
special position and has an overall octahedral coordination derived from the symmetry
˚
˚
˚
operations (Te1–Cl1 ¼ 2.509(2) A, Te1–Cl2 ¼ 2.526(2) A, Te1–Cl3 ¼ 2.5455(16) A). The
Cl–Te–Cl bond angles between two trans Te–Cl bonds are 180ꢃ, whereas those for cis
Te–Cl bonds deviate slightly from the ideal 90ꢃ, in the range of 88.45(7)– 93.05(12)ꢃ.
The structure of 2 also reveals the formation of a 2-D network and may be described
as the interconnection of 1-D networks composed of L1 assemblies by [TeCl6]2ꢂ. The
crystallographically unique chloride is again held between two protonated amine
˚
nitrogens of L1. The N ꢀ ꢀ ꢀ N distance of 5.2 A between two nitrogens in one ligand and
localization of two acidic protons on L1 allows recognition of chloride, as template
acceptor, through a chelating mode of N–H ꢀ ꢀ ꢀ Cl interactions with protonated L1
ꢃ
ꢃ
˚
˚
(N1–H1 ꢀ ꢀ ꢀ Cl4 ¼ 3.105 A, 172.7 ; N2–H2 ꢀ ꢀ ꢀ Cl4 ¼ 3.244 A, 165.03 ). Similar as 1, the
interconnection of neighboring L1’s also forms an encapsulation assembly through
weak C–H ꢀ ꢀ ꢀ Cl hydrogen bonds, in which every two chlorides are encapsulated by two
˚
L1’s, and the approximate region for the inclusion of chloride is 6.9 A (defined by H34
˚
and H34) ꢅ 6.2 A (defined by H31A and H31A). The encapsulation assemblies are

2230
F. Guo et al.
(a)
(b)
(c)
Figure 2. (a) Crystal structure of 2; (b) the formation of 1-D molecular layer along the ac plane; and
(c) crystal packing of 2 along the a-axis. For the sake of clarity only hydrogens involved in H-bonding are
represented.
connected through C–H ꢀ ꢀ ꢀ ꢈ interactions (C27–H27A ꢀ ꢀ ꢀ C9: 3.609 A, 135.3ꢃ,
˚
˚
H27A ꢀ ꢀ ꢀ C9: 2.888 A), leading to an infinite 1-D network along the ac plane, as seen
in figure 2(b).
Due to the different conformation of L1 in 2 and the different choice of primary
metal ions compared with 1, the crystal 2 gives different crystal packing (figure 2c).

Supramolecular inclusion solids
2231
Figure 3. The conformation comparison of L1 in crystals 1 and 2.
In 2, eight weak C–H ꢀ ꢀ ꢀ Cl hydrogen bonds construct the second-sphere coordination
between [TeCl6]2ꢂ and the ligand (table 2). The chloride of the longest Te–Cl bond, Cl3,
is a hydrogen-bond acceptor, linking molecules of ligand at (ꢂx, ꢂy, 1 ꢂ z) and (1 þ x,
ꢃ
˚
1 þ y, z) through two weak C–H ꢀ ꢀ ꢀ Cl interactions [C3–H3A ꢀ ꢀ ꢀ Cl3: 3.670 A, 149.8 ,
ꢃ
˚
˚
˚
H3A ꢀ ꢀ ꢀ Cl3 ¼ 2.836 A; C38–H38A ꢀ ꢀ ꢀ Cl: 3.738 A, 154.9 , H38A–Cl ¼ 2.874 A]. In
addition, the chloride of the second longest Te–Cl bond, also a hydrogen-bond
ꢃ
˚
acceptor, has two weak C–H ꢀ ꢀ ꢀ Cl interactions [C8–H8B ꢀ ꢀ ꢀ Cl2: 3.713 A, 163.9 , H8B–
ꢃ
˚
˚
Cl2 ¼ 2.770 A; C22–H22B ꢀ ꢀ ꢀ Cl3: 3.785, 155.1 , H22B–Cl3 ¼ 2.892 A] with the mole-
cules of ligand at (ꢂx, ꢂy, 1 ꢂ z) and (1 þ x, 1 þ y, z). The remaining short Te–Cl bond
was not involved in any interactions.
3.3. Conformation comparison of L1 in crystals 1 and 2
Molecules of diprotonated L1 exhibit distinct conformations in the two crystals viewed
from the projection of the Newman-type overlay of two nitrogens (figure 3). For 1, the
two phenyl rings (denoted 1 and 2) on one side are parallel with the dihedral angle of
3.4ꢃ, and the other two phenyl rings (denoted 3 and 4) on the other side are crossed with
the dihedral angle of 54.2ꢃ, whereas for 2, the two phenyl rings on one side are almost
vertical, with the dihedral angle of 85.8ꢃ, and the other two phenyl rings on the other
side are arranged with the dihedral angle of 68.4ꢃ. Such different conformation of L1
results in the different crystal packing in 1 and 2.
3.4. Thermal analysis
Thermogravimetric analyses (TGA) were carried out on 1 and 2. In figure 4, loss of H2O
from the cavity of 1 was slow, beginning at room temperature to 190ꢃC (5.14% calcd,
5.48% obsd). This merges with a second mass loss from 190ꢃC to 500ꢃC, which was
considered decomposition of the ligand and HCl (80.21% Calcd, 79.52% obsd). The mass
loss above 500ꢃC was further decomposition of CuCl4. TGA of 2 shows a weight loss
from 200ꢃC to 400ꢃC, as seen in figure 4(b), from decomposition of the ligand and HCl
(76.76% calcd, 74.44% obsd). The mass loss above 400ꢃC was decomposition of TeCl6.
4. Conclusions
A number of complexes containing CuX2 have been published in the past years. One
type is A2[CuX4] [23, 24], where A is usually organic protonated bases and X is Cl

2232
F. Guo et al.
Figure 4. The TG of 1 (a) and 2 (b).
or Br. In addition, using the ‘‘plasticity’’ of the coordination sphere of Cu(II), various
coordination polymers containing [CuX4] have also been constructed, such as the
structure of {[Cu(bpea)Cl]2CuCl4} (bpea ¼ N-bis(2-pyridylmethyl)ethylamine) [25].
These molecules containing [CuX4]2ꢂ are well-studied because they can offer possible
mechanisms for magnetic exchange. With regard to the anion recognition
supramolecules, some metal ions, as guest molecules, can be encapsulated inside the
designed host, for example, the ucurbit[5]uril as the macrocyclic cryptand can include
[PbCl6]4ꢂ or [HgCl4]2ꢂ [26]. Meanwhile, metal coordination receptors can be
specificꢂally deꢂsigned as artificial hosts for polyatomic anion recognition [27], such
as NO3 , ClO4 , BFꢂ4 , PFꢂ6 , and SO42ꢂ. Herein, we have proposed the approach of
second-sphere coordination into the construction of supramolecular inclusion solids
with anion species using a diamine ligand and [CuCl4]2ꢂ and [TeCl6]2ꢂ to form
inclusion host, in which guest molecules, such as chloride anions and water, were
contained.
The structure determination revealed that 2-D networks are formed in both
complexes by interconnection of 1-D networks through multiple C–H ꢀ ꢀ ꢀ Cl hydrogen
bonding between metal ions and ligands. Future objectives are directed toward the
design of other ligands that comprise larger space so as to encapsulate a variety of
anions with different sizes and geometries.

Supramolecular inclusion solids
2233
Acknowledgments
This work was supported by the National Science Foundation of China (No. 20772054,
20903052) and the Scientific Research Foundation for the Returned Overseas Chinese
Scholars, State Education Ministry.
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